KR101098516B1 - Adhesive composition and rubber enhancing fiber treated using its - Google Patents

Abstract

The present invention relates to an adhesive composition for rubber reinforcing fiber treatment and a rubber reinforcing fiber treated with the composition, comprising an epoxy compound comprising two or more epoxy groups, an aromatic compound containing a hydroxyl group, and a secondary or tertiary amine compound. It provides an adhesive composition comprising. The present invention also provides a rubber reinforcing fiber obtained by treating the fiber during the spinning or stretching process using the adhesive composition.

Since the adhesive composition of the present invention has excellent solution stability and reactivity, it is easy to process rubber reinforcing fibers, and the obtained rubber reinforcing fibers have excellent adhesion with natural or synthetic rubbers, and thus are applied to rubber products such as tires, belts, and hoses. Effectively increase the physical properties.

Rubber reinforcing fibers, epoxy, aromatics, amines, adhesion

Description

Adhesive composition and rubber reinforcing fiber treated with the composition TECHNICAL FIELD

The present invention is to improve the adhesion between the rubber reinforcing fibers and the rubber composition by treating the rubber reinforcing fibers with an adhesive composition containing an epoxy compound, an aromatic compound containing a hydroxyl group and an amine compound rubber that the adhesion and compatibility is increased An adhesive composition for reinforcing fiber treatment and a rubber reinforcing fiber treated with the composition.

Rubber is largely divided into natural rubber and synthetic rubber. Since rubber has excellent physical properties such as elasticity, rubber is widely used in modern industrial fields such as tires, belts, and hoses. However, while rubber has excellent elasticity, low mechanical properties such as strength and rigidity are added to supplement the reinforcing material.

The rubber reinforcing material is mainly reinforcing fibers (reinforcing fibers, or reinforcing fibers) of twisted yarn cord, polyester fibers represented by polyethylene terephthalate (polyester), nylon (Nylon) Polyamide fibers (polyamide fibers), poly (vinylalcohol) fibers and the like are used. However, the reinforcing fibers have poor adhesiveness with the rubber to be applied, and require separate adhesives.

According to Japanese Patent Application No. 46-11251, 2,6-bis (2 ', 4'-dihydroxyphenylmethyl) -4-chlorophenyl (2,6-bis (2', 4'-dihydroxyphenylmethyl) -4 Reaction product of halogenated phenol such as chlorophenyl and resorcinol / formaldehyde as initial condensate of resorcinol / formaldehyde and rubber latex, etc. (Resorcinol Formaldehyde Latex, Is presented.

When using the RFL treatment liquid, the components of the RFL must be present to some extent on the surface of the reinforcing fibers so that the reinforcing fibers obtain sufficient adhesion (pulling force, adhesion) over a predetermined range after treatment.

In addition, halogenated phenols such as 2,6-bis (2,4-dihydroxylphenylmethyl) -4-chlorophenyl (commonly abbreviated as "packs") use ammonia water to enhance the adhesion effect. A large amount of alkaline components of the ammonia water remain in the reinforcing fibers, causing hydrolysis of the reinforcing fibers. Moreover, in view of the fact that the hydrolysis phenomenon is promoted by heat, the reinforcing fibers treated with the treatment liquid have a problem that the adhesive strength is greatly lowered after heat aging.

In addition, U.S. Patent No. 3,234,067 improves the adhesion of reinforcing fibers to rubber by coating the surface of the reinforcing fibers with an adhesive based on epoxy, isocyanates, and halogenated phenol compounds. It says it can. Specifically, the polyester fiber, which is a reinforcing fiber, is treated with a first treatment liquid consisting of a mixture of an epoxy compound and a diisocyanate blocked with caprolactam or phenol, followed by a second treatment liquid consisting of RFL. A double dipping system is proposed.

However, RFL used as the second treatment liquid has poor compatibility with the diisocyanate of the first treatment liquid, so that the dispersion stability is lowered, and when heat is applied during coating of the reinforcing fibers obtained after the treatment, phenol or capro as the blocking compound It is not preferable because a problem harmful to the environment such as lactam or the like generates harmful gases occurs.

In order to solve the problems of the prior art as described above, the present invention can not only suppress the deterioration of the adhesive force when mixing the rubber composition and rubber reinforcing fibers, but also shorten the standing time after weaving to increase spinning operation and post-processing properties. It is an object to provide an adhesive composition for rubber reinforcing fiber treatment.

It is another object of the present invention to provide a rubber reinforcing fiber treated using the adhesive composition.

In order to achieve the above object, the present invention

Epoxy compounds containing two or more epoxy groups in one molecule;

Aromatic compounds containing a hydroxyl group; And                     

It provides an adhesive composition for rubber reinforcing fiber treatment containing an amine compound.

Preferably, the adhesive composition comprises 1 to 50 parts by weight of an aromatic compound containing a hydroxyl group and 0.1 to 20 parts by weight of an amine compound based on 100 parts by weight of an epoxy compound.

The present invention also provides a rubber reinforcing fiber surface-treated using the adhesive composition.

At this time, the rubber reinforcing fiber is preferably a polyester resin, polyimide resin, polyamide resin and polyvinyl alcohol resin of polyethylene terephthalate and polybutylene terephthalate.

The present invention is described in more detail below.

The present invention provides an adhesive composition for treating rubber reinforcing fibers for increasing the adhesion between the rubber reinforcing fibers and the rubber compositions used to increase the physical properties of rubber compositions such as tires, belts and hoses.

을 포함하는 물질로서, 경화 후 반응 수축이 매우 작고 기계적 성질 및 내마모성, 치수 안정성이 매우 우수하다. 상기 에폭시 화합물은 가교 반응을 수행하기 위하여 1 분자 중에 2 개 이상의 에폭시기를 함유하는 것이 바람직하며, 고온에서 가공 시 상기 화합물 자체가 휘발하는 경우가 있는 바, 그 분자량은 100 이상으로 하는 것이 바람직하다.First, the epoxy compound as the first component of the adhesive composition according to the present invention is an epoxy bond in the molecular structure

As a material containing, the reaction shrinkage after curing is very small, mechanical properties and wear resistance, dimensional stability is very excellent. In order to perform the crosslinking reaction, the epoxy compound preferably contains two or more epoxy groups in one molecule, and the compound itself may volatilize when processed at high temperature, and the molecular weight thereof is preferably 100 or more.

The epoxy compound as the first component can be suitably used within the range of the epoxy group and the molecular weight as long as it is commonly used in the art. For example, the usable epoxy compound may be a general bisphenol A type epoxy (Bisphenol A Type Epoxy); Bisphenol F Type Epoxy; Novolac type epoxy; Flame retardant epoxy; Cyclic aliphatic epoxy (Cycloaliphatic Epoxy); Rubber modified epoxy (Rubber Modified Epoxy); Aliphatic Polyglycidyl Type Epoxy; And glycidyl amine type epoxy (Glycidylamine Type Epoxy).

The epoxy compound may include glycerol, pentaerythritol, sorbitol, ethylene glycol, ethylene glycol, propylene glycol, and polypropylene glycol. obtained by reacting a polyhydric alcohol such as propyleneglycol) with a halogen-containing epoxide compound such as epichlorohydrin, resorcinol, bis (4-hydroxyphenyl) diethylethane (bis ( 4-hydroxyphenyldiethylethane), phenol-formaldehyde resin and resorcinol-formaldehyde resin, cresol resin, novolac resin, bisphenol A It is obtained by making polyhydric phenols, such as a bisphenol A type resin, react with the said halogen containing epoxide compound.

Preferably, the epoxy compound as the first component of the present invention should take into account the degree of crosslinking reaction closely related to the adhesion ability, so as to be 0.1 to 2.0% by weight of the rubber reinforcing fiber to be treated. In this case, when the content of the epoxy compound is less than the above range, even if the crosslinking reaction of the epoxy compound is ideally performed, the content is small, resulting in a problem that the adhesion between the final fiber and rubber is lowered. In addition, if the above range is exceeded, excessive crosslinking may cause a drop in the process of the epoxy compound, and even if the spinning workability is greatly reduced, a defect such as foreign matters may occur during post-processing such as weaving.

In particular, the aromatic compound containing a hydroxyl group as the second component of the adhesive composition according to the present invention includes at least one hydroxyl group (OH) in the molecular structure to increase adhesion through condensation reaction with the epoxy compound as the first component, and In the case of the subsequent process also reacts with RFL (Resorcinol Formaldehyde Latex) to further increase the adhesion.

The aromatic compound containing a hydroxyl group as the second component is preferably a substance exhibiting acidity in order to facilitate compatibility with other substances, for example, dispersion, and to suppress hydrolysis of rubber reinforcing fibers. In the present invention, it is selected from the group consisting of phenol, resorcinol, salicylic acid, p-chlorophenol and resorcinol formaldehyde condensation product alone or a mixture thereof. .

Preferably, the aromatic compound containing a hydroxyl group which is the second component of the present invention is suitably 1 to 50.0 parts by weight based on 100 parts by weight of the epoxy compound as the first component in consideration of adhesion and dispersibility. At this time, if the content of the second component is less than the above range can not be expected to improve the adhesion according to the addition of the compound at all, if it exceeds the above range, the first component capable of reacting with the aromatic compound is an epoxy compound and a subsequent process The condensation reaction with the RFL compound proceeds excessively, so that the solubility in water used as a diluent is very low, so that the dispersibility is lowered, resulting in a decrease in solution stability of the final adhesive treatment liquid obtained.

In addition, the amine compound as the third component according to the present invention serves as a catalyst for increasing the crosslinking reaction rate of the epoxy compound. For example, by increasing the reaction rate of the carboxyl group terminal contained in the polyester fiber of the rubber reinforcing fiber and the epoxy compound of the first component, shortening period of the treated fibers and at the same time containing the hydroxyl group of the epoxy compound and the second component It increases the reactivity with the aromatic compound. As the amine compound, secondary and tertiary amine compounds may be preferably used, and more preferably tertiary amine compounds are used.

The secondary amine compound may include dialkylamine such as diethylamine, dipropylamine, diethanolamine, diethanolamine, and dialcoholamine such as dipropanolamine. The tertiary amine compound may be trialkylamine such as triethylamine, tripropylamine, and triethanolamine and tripropanolamine. Alcohol amines (trialcoholamine) and the like.

Preferably, the amine compound as the third component of the present invention contains 0.1 to 20.0 parts by weight based on 100 parts by weight of the epoxy compound as the first component in consideration of the reaction rate of the epoxy compound and the like. In this case, when the content of the amine compound is less than the above range, the increase in the reaction rate due to the addition of the amine compound cannot be expected, and thus the standing time of the fiber to be treated becomes long. On the other hand, when the content of the amine compound exceeds the above range, the reaction rate of the epoxy compound contained in the treatment solution is excessively increased, resulting in a drop in the process of the epoxy compound due to excessive crosslinking reaction, thereby greatly reducing the spinning workability.

As such, the adhesive composition for treating the rubber reinforcing fiber of the present invention comprises an epoxy compound, an aromatic compound containing a hydroxyl group and an amine compound as the first to third essential components, and the rubber reinforcing fiber using the obtained adhesive composition Carry out surface treatment.

The rubber reinforcing fiber is used to increase the physical properties of the rubber product, and is treated with the adhesive composition according to the present invention to include a functional group having an adhesive ability such as an epoxy group on the surface of the rubber reinforcing fiber, thereby excellent adhesion when mixed with the rubber composition It can significantly increase the mechanical properties of the rubber composition.

Such rubber reinforcing fibers may be any fiber conventionally used for increasing the physical properties of the rubber composition, for example, polyethylene terephthalate (poly (ethyleneterephthalate)) and polybutylene terephthalate (poly (buthyleneterephthalate) and the composition Polyester resins such as treated rubber reinforcing fibers); Polyimide resins; Polyamide resins; And it is selected from the group consisting of poly (vinylalcohol) resins, preferably using a polyester resin.

At this time, the molecular weight of the rubber reinforcing fibers, denia, the number of filaments, the cross-sectional shape, the yarn properties, the fine structure, the presence or absence of additives, polymer properties such as terminal carboxyl concentration, etc. are not particularly limited in the present invention.

In order to process the rubber reinforcing fibers using the adhesive composition according to the present invention, after the spinning oil is dispersed, the adhesive composition is added thereto to form an adhesive treatment liquid. Manufacture.

The spinning emulsion is not particularly limited in the present invention, and may be appropriately selected depending on the rubber reinforcing fiber to be used. The spinning oil may be emulsified with natural oils such as palm oil and castor oil, ester oils of higher alcohols or polyhydric alcohols with higher fatty acids, synthetic oils such as alkyl polyethers, lubricants of such synthetic oils, and smoothing agents. Surfactant to be dispersed and antistatic agents, heat-resistant and / or colorants, etc. may be used in combination.

In this case, generally, the surfactant may be a compound obtained by adding alkylene oxide to castor oil or higher alcohol, or an ester oil of polyethylene (or polypropylene) oxide or polyethylene glycol and higher fatty acid.

As described above, the method for treating rubber reinforcing fibers using the adhesive treatment agent containing the adhesive composition is not particularly limited in the present invention, and is known in the art.

For example, the treatment of rubber reinforcing fibers using the adhesive treatment agent according to the present invention alone; After treatment of the adhesion treatment agent, treatment in two steps using a post treatment agent such as RFL; Various methods such as pretreatment after mixing the adhesion treatment agent and RFL, followed by two steps of posttreatment with RFL solution may be used.

As a treatment method using such an adhesive treatment agent, conventional methods such as immersing, applying, or spraying a rubber reinforcing fiber to increase the adhesive ability to the adhesive treatment agent are employed.

Following the above process, the obtained rubber reinforcing fibers are dried in an oven or the like and heat-treated so that the solid content of the adhesive composition adhered to the surface of the rubber reinforcing fibers after drying is 3 to 8% (weight ratio). At this time, the drying and heat treatment is carried out drying for 70 to 200 seconds at 70 to 100 ℃, then heat treatment for 30 to 120 seconds at a temperature of 210 to 250 ℃.

As a result, rubber reinforcing fibers coated with the adhesive composition according to the present invention on the surface can be obtained, and the obtained rubber reinforcing fibers are mixed with the rubber composition in a subsequent process to increase the physical properties of the rubber composition.

On the other hand, the surface treatment of the rubber reinforcing fibers can be treated in two steps using a separate adhesive composition, such as RFL.

This treatment method is simplified, and is made by heat treatment after surface coating with the adhesive composition according to the present invention, followed by coating the RFL treatment solution and heat treatment similar to the above-described process. However, at this time, the treatment time using the treatment solution should be appropriately adjusted such that the content of the adhesive solids present on the surface of the rubber reinforcing fiber is in the range of 3 to 8%.

As described above, the rubber reinforcing fibers according to the present invention can be used in the production of rubber products such as tires, belts and hoses to exhibit excellent adhesion with the rubber composition, resulting in effectively increasing the physical properties of the final rubber product.

According to a preferred embodiment of the present invention, an epoxy compound is used, and resorcinol, salicylic acid and RFL condensate are applied as an aromatic compound containing a hydroxyl group, and in addition, an adhesive composition including an amine compound is prepared.

Surface treatment of the polyester cord (cord) as a rubber reinforcing fiber using the obtained adhesive composition, and measured the adhesive strength after two weeks was confirmed that the adhesion between the rubber reinforcing fibers and the rubber composition according to the present invention is excellent. (See Table 3). In addition, as a result of checking the processability such as spinning operation through the process, in the case of the comparative example deviated from the composition of the present invention, the long-term spinning operation such as the epoxy compound is accumulated on the Godt Roller, which is very poor, the present invention In the case of the embodiment according to the above-described problems rarely occur or appeared to be insignificant.

Thus, the rubber reinforcing fiber treated with the adhesive composition according to the present invention increases the adhesiveness with the rubber composition, it is possible to obtain sufficient adhesion even in a small amount can effectively increase the mechanical properties of the rubber composition.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the following examples are only examples of the present invention, and the present invention is not limited to these examples.

Example 1 Preparation of Polyester Rubber Reinforcement Fiber

A polyester chip having an intrinsic viscosity of 1.03 (measured at 30 ° C. in a mixed solvent of phenol: tetrachloroethane = 3: 2) was subjected to a spinning temperature of 305 ° C. at a hole diameter of 0.4 mm and a hole count of 220 g in a spinneret of 192. The undrawn yarn was obtained by spinning at a discharge amount of / min, and the obtained undrawn yarn was cooled to a temperature below the secondary transition point of the polymer, and a spinning emulsion treatment liquid was applied by using an ordinary oiling roller.

As the spinning emulsion treatment liquid, one obtained by dissolving 12 kg of an oil for polyester having a fatty acid ester and a nonionic surfactant as a main component in 80 kg of water was used.

Next, it was introduced into a direct spinning machine of a five-stage goth roller in order to draw the unstretched polyester fiber, and using an oil jet between the five-stage goth roller and the winder The adhesive composition according to the invention was sprayed onto the polyester fibers. At this time, the degree of spraying was sufficiently buried so that the epoxy emulsifier liquid fell in the polyester cord so that the adhesive liquid of 3 to 8% (solid content) was attached.

The adhesive composition of Example 1 used above was prepared by reacting glycerine and epichlorohydrin with 8 kg of EPON812 ^TM , 0.4 kg of resorcinol, 0.08 kg of diethanolamine, and 0.1 kg of nonionic surfactant. Dissolve in kg to prepare an adhesive composition.

In the drawing process, the temperature and line speed of the direct spinning stretching machine Godet roller are 80 ° C-400 m / min for the first step roller, 100 ° C-410 m / min for the second step roller, 110 ° C-1600 m / min for the three step roller, respectively. Four-stage roller 200 ° C.-2000 m / min, and five-stage roller room temperature-1980 m / min.

Subsequently, the polyester fibers obtained after the stretching step were heat treated at 150 ° C. for 2 minutes and at 220 ° C. for 2 minutes to prepare polyester fibers for rubber reinforcement.

Example 2 Preparation of Polyester Rubber Reinforcement Fiber

The adhesive composition was carried out in the same manner as in Example 1 except that 20 kg of ECN1400 ^™ , 0.4 kg of resorcinol, 0.2 kg of diethanolamine, and 0.1 kg of a nonionic surfactant were dissolved in 80 kg of water. Ester rubber reinforcing fibers were prepared. At this time, the ECN1400 ^TM is a compound (concentration 40%) obtained by reacting with a cresol novolak resin and epichlorohydrin manufactured by CIBAGEIGY.

Example 3 Preparation of Polyester Rubber Reinforcement Fiber

Polyester rubber was prepared in the same manner as in Example 1, except that 8 kg of EPON812 ^™ , 2.0 kg of salicylic acid, 0.2 kg of diethanolamine, and 0.1 kg of a nonionic surfactant were dissolved in 92 kg of water. Reinforcing fibers were prepared.

Example 4 Preparation of Polyester Rubber Reinforcing Fibers

Polyester rubber reinforcing fiber was carried out in the same manner as in Example 1, except that 8 kg of EPON812 ^™ , 2.0 kg of salicylic acid, 0.08 kg of triethanolamine, and 0.1 kg of nonionic surfactant were dissolved in 92 kg of water. Was prepared.

Example 5 Preparation of Polyester Rubber Reinforcement Fibers

Polyester rubber reinforcing fiber was carried out in the same manner as in Example 1, except that 8 kg of EPON812 ^™ , 2.0 kg of salicylic acid, 0.4 kg of triethanolamine, and 0.1 kg of nonionic surfactant were dissolved in 92 kg of water. Was prepared.

Example 6 Preparation of Polyester Rubber Reinforcement Fiber

Polyester rubber reinforcing fiber was carried out in the same manner as in Example 1, except that 8 kg of EPON812 ^™ , 2.0 kg of salicylic acid, 1.2 kg of triethanolamine, and 0.1 kg of nonionic surfactant were dissolved in 92 kg of water. Was prepared.

Example 7 Preparation of Polyester Rubber Reinforcing Fibers

Polyester rubber was prepared in the same manner as in Example 1, except that 8 kg of EX-614 ^TM , 0.8 kg of salicylic acid, 0.4 kg of triethanolamine, and 0.1 kg of nonionic surfactant were dissolved in 92 kg of water. Reinforcing fibers were prepared. At this time, the EX-614 ^TM is a compound obtained by reacting glycerin and epichlorohydrin manufactured by NAGASE.

Example 8 Preparation of Polyester Rubber Reinforcement Fiber

Polyester rubber was prepared in the same manner as in Example 1, except that 8 kg of EX-614 ^TM , 0.8 kg of salicylic acid, 16 kg of triethanolamine, and 0.1 kg of nonionic surfactant were dissolved in 92 kg of water. Reinforcing fibers were prepared.

Example 9 Preparation of Polyester Rubber Reinforcement Fiber

Polyester rubber reinforcement was carried out in the same manner as in Example 1, except that 4 kg of EPON812 ^™ , 2.0 kg of salicylic acid, 0.04 kg of triethanolamine, and 0.1 kg of nonionic surfactant were dissolved in 92 kg of water as an adhesive composition. Fibers were prepared.

Example 10 Preparation of Polyester Rubber Reinforcement Fibers

Polyester rubber reinforcement was carried out in the same manner as in Example 1, except that 16 kg of EPON812 ^™ , 1.6 kg of salicylic acid, 0.16 kg of triethanolamine, and 0.1 kg of nonionic surfactant were dissolved in 92 kg of water as an adhesive composition. Fibers were prepared.

Comparative Example 1: Preparation of Polyester Cord Treated with RFL Adhesive

In order to compare the adhesion with RFL used as a conventional adhesive composition was carried out as follows.

First, as a spinning emulsion treatment liquid, one obtained by dissolving 12 kg of an oil for polyester and 8 kg of an epoxy compound EPON812 mainly composed of a fatty acid ester and a nonionic surfactant was dissolved in 80 kg of water.

Next, it was carried out in the same manner as described above in Example 1, wherein the composition as shown in Table 1 as the adhesive composition, resorcinol, formaldehyde and sodium hydroxide and styrene / 1,3-butadiene / vinylpyridine (15:70:15) was dispersed in water to prepare a RFL adhesive composition for a tire cord at 20% concentration.

Raw material name weight% Resocinol 8.8 Formaldehyde (37%) 4.76 NaOH (10%) 10 Styrene / 1.3-butadiene / vinyl pyridine rubber (41%) 56 water 17.6

Comparative Example 2: Preparation of Polyester Rubber Reinforcement Fiber

Polyester rubber reinforcing fibers were prepared in the same manner as in Example 1, except that 8 kg of EPON812 ^™ and 0.1 kg of nonionic surfactant were dissolved in 92 kg of water as an adhesive composition.

Comparative Example 3: Preparation of Polyester Rubber Reinforcement Fiber

Polyester rubber was prepared in the same manner as in Comparative Example 2, except that 8 kg of EPON812 ^™ , 0.8 kg of salicylic acid, and 0.1 kg of nonionic surfactant were dissolved in 86 kg of water so as not to include an amine compound as the adhesive composition. Reinforcing fibers were prepared.

Comparative Example 4: Preparation of Polyester Rubber Reinforcement Fiber

In the same manner as in Comparative Example 2, except that 8 kg of EPON812 ^™ , 0.8 kg of salicylic acid, 2.4 kg of triethanolamine, and 0.1 kg of a nonionic surfactant were dissolved in 86 kg of water to contain an excess of an amine compound as an adhesive composition. To prepare polyester rubber reinforcing fibers.

Comparative Example 5: Preparation of Polyester Rubber Reinforcement Fiber

Comparative Example 2, except that 8 kg of EPON812 ^TM , 0.8 kg of resorcinol, 4 kg of diethanolamine, and 0.1 kg of a nonionic surfactant were dissolved in 92 kg of water to contain an excess of an amine compound as an adhesive composition. In the same manner as to prepare a polyester rubber reinforcing fiber.

The composition of Example 1 to Comparative Example 5 as described above is as shown in Table 2 below.

division Epoxy adhesive treatment agent Epoxy compound Hydroxyl-containing aromatic compounds Amine compound Nonionic
Interface
Active agent water Kinds content Kinds content Kinds content content content Example 1 EPON812 ¹⁾ 8 kg Resorcinol 0.4 kg Diethanolamine 0.08 kg 0.1 kg 92 kg Example 2 ECN1400 ²⁾ 20 kg Resorcinol 0.4 kg Diethanolamine 0.2 kg 0.1 kg 80 kg Example 3 EPON812 8 kg Salicylic acid 2.0 kg Diethanolamine 0.08 kg 0.1 kg 92 kg Example 4 EPON812 8 kg Salicylic acid 2.0 kg Triethanolamine 0.08 kg 0.1 kg 92 kg Example 5 EPON812 8 kg Salicylic acid 2.0 kg Triethanolamine 0.4 kg 0.1 kg 92 kg Example 6 EPON812 8 kg Salicylic acid 2.0 kg Triethanolamine 1.2 kg 0.1 kg 92 kg Example 7 EX-614 ³⁾ 8 kg Salicylic acid 0.8 kg Triethanolamine 0.4 kg 0.1 kg 92 kg Example 8 EX-614 8 kg Salicylic acid 0.8 kg Triethanolamine 0.016 kg 0.1 kg 92 kg Example 9 EPON812 4 kg Salicylic acid 2.0 kg Triethanolamine 0.04 kg 0.1 kg 92 kg Example 10 EPON812 16 kg Salicylic acid 1.6 kg Triethanolamine 0.16 kg 0.1 kg 92 kg Comparative Example 1 - - - - - - - - Comparative Example 2 EPON812 8 kg - - - - 0.1 kg 91 kg Comparative Example 3 EPON812 8 kg Salicylic acid 0.8 kg - - 0.1 kg 86 kg Comparative Example 4 EPON812 8 kg Salicylic acid 0.8 kg Diethanolamine 2.4 kg 0.1 kg 86 kg Comparative Example 5 EPON812 8 kg Resorcinol 0.8 kg Diethanolamine 0.004 kg 0.1 kg 92 kg 1) SHELL Corporation; Reaction product of glycerin with epichlorohydrin
2) CIBAGEIGY company; Reaction product of cresol novolac resin with epichlorohydrin (concentration 40%)
3) NAGASE Corporation; Reaction product of glycerin with epichlorohydrin

Test Example

A: Adhesion Test (H-test)

In order to measure the adhesive force of the polyester fiber for rubber reinforcement obtained in the above Examples and Comparative Examples, a rubber composition having a composition as shown in Table 3 below was treated according to the provisions of ASTM D-2138-72 and 60 kg / cm 2 The mixture was vulcanized at 150 ° C. for 30 minutes.

 Subsequently, the vulcanized polyester cord was heat-aged and cut in an oven at 150 ° C. for 76 hours to prepare a specimen, and then drawn out at 25 ° C. at 300 ° C./min with an Intron to obtain adhesion (kgf / 25 mm). ) Was evaluated. The obtained results are as shown in Table 4 below.

Raw material name Addition amount (part) Styrene-Butadiene Rubber
(Styrene-Butadiene Rubber, SBR) 100 Zinc oxide 5 Carbon black 50 Stearic acid One Nectron 60 ^TM 25 Tetramethyl Thiuram Monosulfide
(tetra methyl thiurammonosulfide) 1.5 2-Mercapto benzothiazole 0.5 Yiwu 1.5

B: radiation operation

In order to determine the spinning operation during the preparation of the polyester fiber for rubber reinforcement obtained in Examples and Comparative Examples, the degree of foreign matter sedimentation of the Godet roller was examined, and the obtained results are shown in Table 4 below.

C: Post Processing

In order to determine the post-processability at the time of manufacturing the polyester fiber for rubber reinforcement obtained in the above Examples and Comparative Examples, the degree of foreign matter sedimentation of the body during weaving was examined, and the obtained results are shown in Table 4 below.

division In the drawing company
Epoxy compound
(weight%) Hydroxyl-containing aromatic compounds
(Part by weight) ^*
Amine compound
(Part by weight) ^** Adhesion of 2 Weeks
(kg / cm) Foreign body in Godet roller When spinning When weaving Example 1 0.41 5 One 13.0 radish radish Example 2 0.39 4 2 13.5 radish radish Example 3 0.37 25 One 12.5 radish radish Example 4 0.41 25 One 13.5 radish radish Example 5 0.40 25 5 13.0 radish radish Example 6 0.37 25 15 12.5 radish radish Example 7 0.41 10 5 13.0 radish radish Example 8 0.41 10 0.2 11.0 radish radish Example 9 0.21 10 One 12.0 radish radish Example 10 0.82 10 One 13.5 radish radish Comparative Example 1 0.38 10 - 12.0 U radish Comparative Example 2 0.39 - - 6.0 radish radish Comparative Example 3 0.40 - - 8.0 radish radish Comparative Example 4 0.40 10 30 9.5 radish radish Comparative Example 5 0.40 10 0.05 8.5 radish radish *, ** 100 parts by weight of epoxy compound

According to Table 4, in the case of the polyester cord obtained by treatment with the adhesive composition according to the present invention showed an adhesive force in the range of 11.0 to 13.5 kg / cm, in the comparative example it is not only low adhesion but also foreign matter accumulated on the roller during the process It can be seen that workability is low due to side reactions and unreacted reactions.

Specifically, in the case of Comparative Example 1, as a large amount of the epoxy compound to be processed during processing is laminated on the Godet roller, there is a problem in long-term operability, such as difficult to proceed properly.

In addition, in the case of Comparative Example 2 it was found that by omission of both the heat treatment and the catalyst after the epoxy compound treatment, as the reaction between the initial epoxy compound and the polyester end group proceeded slowly, the adhesive strength was severely insufficient at 6 kg / cm.

Furthermore, in the case of Comparative Example 3, the curing reaction rate of the epoxy compound was slow due to not using the amine compound serving as a catalyst, and thus the degree of improvement was not sufficient.

In addition, in the case of Comparative Example 4 by using an excess of the amine catalyst was accompanied by a side reaction of the epoxy compound it can be seen that the improvement effect of using the catalyst is halved.

As described above, according to the present invention, the rubber composition and the rubber reinforcing fiber excellent in adhesion performance were obtained, and an adhesive composition including an epoxy compound, an aromatic compound containing hydroxyl group, and an amine compound was prepared to increase the adhesion ability. .

By the adhesive composition of the present invention, the present invention can not only suppress the deterioration of the adhesive strength when mixing the rubber composition and rubber reinforcing fibers, but also shorten the leaving time after weaving to obtain the effect of increasing the spinning operation and post-processability. Could.

In addition, the obtained rubber reinforcing fibers can increase the adhesiveness with the rubber composition, can obtain a sufficient adhesion even in a small amount can effectively increase the mechanical properties of the rubber composition. In addition, even if the heat treatment after the adhesive treatment of the rubber reinforcing fiber does not generate a harmful substance such as conventional phenol is improved in terms of the environment.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention as defined by the following claims It can be understood that

Claims (8)

Epoxy compounds containing two or more epoxy groups in one molecule; Group consisting of phenol, resorcinol, salicylic acid, p-chlorophenol and resorcinol formaldehyde condensation product alone and mixtures thereof Aromatic compounds containing at least one hydroxyl group selected from among them; And An amine compound, An adhesive composition for treating rubber reinforcing fibers, comprising 1 to 50 parts by weight of an aromatic compound containing a hydroxyl group and 0.1 to 20 parts by weight of an amine compound, based on 100 parts by weight of the epoxy compound. The method of claim 1, wherein the adhesive composition is based on 100 parts by weight of the epoxy compound, An adhesive composition comprising 5 to 25 parts by weight of an aromatic compound containing a hydroxyl group and 0.2 to 15 parts by weight of an amine compound. The adhesive composition of claim 1, wherein the epoxy compound has a molecular weight of 100 daltons or more. delete The adhesive composition of claim 1, wherein the amine compound is selected from secondary or tertiary amine compounds. The method of claim 5, wherein the secondary amine compound is at least one compound selected from the group consisting of diethylamine, dipropylamine, diethanolamine and dipropanolamine, The tertiary amine compound is an adhesive composition, characterized in that at least one compound selected from the group consisting of triethylamine (triethylamine), tripropylamine (tripropylamine), triethanolamine (triethanolamine) and tripropanolamine (tripropanolamine). Epoxy compounds containing two or more epoxy groups in one molecule; Group consisting of phenol, resorcinol, salicylic acid, p-chlorophenol and resorcinol formaldehyde condensation product alone and mixtures thereof Aromatic compounds containing at least one hydroxyl group selected from among them; And An amine compound, A rubber reinforcing fiber treated with an adhesive composition for treating rubber reinforcing fibers, comprising 1 to 50 parts by weight of an aromatic compound containing a hydroxyl group and 0.1 to 20 parts by weight of an amine compound, based on 100 parts by weight of the epoxy compound. The method of claim 7, wherein the adhesive composition is based on 100 parts by weight of the epoxy compound, A rubber reinforcing fiber comprising 5 to 25 parts by weight of an aromatic compound containing a hydroxyl group and 0.2 to 15 parts by weight of an amine compound.